A kinetic modeling study is presented for batch nitroxide mediated polymerization (NMP) of methyl methacrylate (MMA; nitroxide: N‐tert‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] (SG1)). Arrhenius parameters for SG1 disproportionation (A = 1.4 10⁷ L mol⁻¹ s⁻¹; E_a = 23 kJ mol⁻¹) are reported, based on homopolymerization data accounting for unavoidable temperature variations with increasing time, that is, nonisothermicity. For low targeted chain lengths (TCLs ≤ 300), this nonisothermicity is also relevant for NMP of MMA with a small amount of styrene. Parameter tuning to copolymerization data confirms a penultimate monomer unit effect for activation (s_a2 = k_a12/k_a22=6.7; 363 K; 1: MMA; 2: styrene). To obtain, for a broad TCL range (up to 800), a dispersity well below 1.3 an initial styrene mass fraction of ca. 10% is required. An interpretation of the comonomer incorporation is performed by calculating the fractions of activation‐growth‐deactivation cycles with a given amount of monomer units and the copolymer composition distribution. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2545–2559, 2018

中文翻译：

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评估甲基丙烯酸甲酯NMP中SG1歧化和添加苯乙烯的影响

进行了动力学模拟研究，用于甲基丙烯酸甲酯（MMA;氮氧化物：N-叔丁基-N- [1-二乙基膦酰基-（2,2-二甲基丙基）]（SG1））的间歇硝化介导聚合（NMP）。基于均聚数据，报告了SG1歧化的Arrhenius参数（A = 1.4 10 ⁷ L mol ^-1 s ^-1； E _a  = 23 kJ mol ^-1），原因是随着时间的推移不可避免的温度变化，即非等温性。对于低目标链长（TCL≤300），这种非等温性也与含有少量苯乙烯的MMA的NMP有关。对共聚数据进行参数调整可确认激活的倒数第二个单体单元效应（s _a2  = k _a12/ k _a22 = 6.7; 363 K；1：MMA；2：苯乙烯）。为了获得宽的TCL范围（最高800），分散度要远低于1.3，苯乙烯的初始质量分数约为1。要求为10％。对共聚单体掺入的解释是通过计算活化-生长-失活循环的分数（在给定的单体单元数量和共聚物组成分布的情况下）来进行的。©2018美国化学工程师学会AIChE J，64：2545–2559，2018